Thiopheneazo dyes with a coupling component of the diaminopyridine series

ABSTRACT

Azo dyes having the formula ##STR1## wherein the substituents are as defined in the specification and are useful for dyeing or printing textile materials.

This application is a continuation of application Ser. No. 07/967,131,filed on Oct. 27, 1992, now abandoned.

The present invention relates to novel azo dyes of formula I ##STR2##where X is cyano or a radical of the formula COOQ¹ or CONQ¹ Q², whereinQ¹ and Q² are identical or different and singly are, independently ofone another, substituted or unsubstituted C₁ -C₁₂ -alkyl with or withoutinterruption by from 1 to 3 oxygen atoms in ether function, C₅ -C₇-cycloalkyl, C₃ -C₄ -alkenyl, or substituted or unsubstituted phenyl ortogether are, together with the nitrogen atom joining them, a 5-or6-membered saturated heterocyclic radical with or without further heteroatoms or else Q² may be hydrogen,

Y is C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulfonyl, halogen,substituted or unsubstituted phenoxy, substituted or unsubstitutedphenylthio or substituted or unsubstituted phenylsulfonyl,

Z is cyano, nitro, substituted or unsubstituted phenylsulfonyl, C₁ -C₆-alkylsulfonyl, formyl or a radical of the formula --CH═T, wherein T isthe radical of an acidic-CH compound, and

R¹, R² and R³ are identical or different and singly are, independentlyof one another, substituted or unsubstituted C₁ -C₁₂ -alkyl, with orwithout interruption by from 1 to 3 oxygen atoms in ether function, C₅-C₇ -cycloalkyl, substituted or unsubstituted phenyl, C₃ -C₆ -alkenyl,substituted or unsubstituted benzoyl, C₁ -C₈ -alkanoyl, C₁ -C₆-alkylsulfonyl or substituted or unsubstituted phenylsulfonyl or R² andR³ together are, together with the nitrogen atom joining them, a 5- or6-membered saturated heterocyclic radical with or without further heteroatoms,

excepting the following compounds: ##STR3## A) Y=chlorine, Z=formyl, R¹=C₃ H₆ OC₂ H₄ OC₆ H₅, R², R³ =CH₃,

B) Y=chlorine, Z=(NC)₂ C═CH--, R¹ =C₃ H₆ OC₂ H₅, R², R³ =C₂ H₅,

C) Y=chlorine, Z=(NC)₂ C═CH--, R¹ =C₃ H₆ OC₂ H₄ OC₂ H₄ OC₆ H₅, R², R³=C₂ H₅,

D) Y=chlorine, Z=(NC)₂ C═CH--, R¹ =C₄ H₈ OC₄ H₉, R², R³ =C₂ H₅,

E) Y=chlorine, Z=(NC)₂ C═CH--, R¹ =C₃ H₆ OC₂ H₄ OC₆ H₅, R², R³ =C₃ H₇,

F) Y=chlorine, Z=C₄ H₉ OOC(NC)C═CH--, R¹ =C₃ H₆ OC₂ H₅, R², R³ =C₂ H₅,

G) Y=chlorine, Z=C₄ H₉ OOC(NC)C═CH--, R¹ =C₃ H₆ OC₂ H₄ OC₆ H₅, R², R³=C₃ H₇,

H) Y=OC₂ H₅, Z=C₂ H₅ OOC(NC)C═CH--, R¹ =C₃ H₆ OCH₃, R², R³ C₂ H₄ OCH₃,

J) Y=OC₂ H₅, Z=C₂ H₅ OOC(NC)C═CH--, R¹ =C₃ H₆ OC₂ H₅, R², R³ =C₂ H₄ OCH₃and

K) Y=OC₂ H₅, Z=C₂ H₅ OOC(NC)C═CH--, R¹ =C₄ H₉, R², R³ =C₂ H₄ OCH₃,

and to a process for dyeing or printing textile materials and dyes basedon thienylazopyridines.

U.S. Pat. No. 4,939,118, which concerns a process for the thermaltransfer of azo dyes having a coupling component of the diaminopyridineseries, also describes the transfer of the dyes mentioned above underthe exceptions A) to K). However, nowhere does the cited document saythat these dyes are also suitable for textile application.

It is true that EP-A-201 896 discloses similar dyes for textileapplication, but these dyes have in each case only primary amino groupson the pyridine ring. Moreover, it has been found that the dyesmentioned in EP-A-201 896 have deficiencies in their applicationproperties.

It is an object of the present invention to provide novel azo dyes on athienylazopyridine basis which are advantageously useful for dyeingtextile fabric. The novel dyes shall in particular possess a good hotlight fastness.

We have found that this object is achieved by the azo dyes of formula Idefined at the beginning.

Any alkyl and alkenyl appearing in the abovementioned formula I may benot only straight-chain but also branched.

Any substituted phenyl groups appearing in the abovementioned formula Imay have as substituents for example C₁ -C₄ -alkyl, chlorine, bromine,nitro or C₁ -C₄ -alkoxy. These phenyl radicals have in general from 1 to3 substituents.

Any substituted alkyl appearing in the abovementioned formula I may haveas substituents for example, hydroxyl, cyclohexyloxy, phenoxy, C₁ -C₄-alkoxycarbonyl, cyano, cyclohexyl or phenyl. These alkyl radicals havein general 1 or 2 substituents.

R¹, R², R³, A¹, A², A³, Q¹ and Q² are each for example methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl,neopentyl, tert-pentyl, hexyl, 2-methylpentyl, hexyl, heptyl, octyl,2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, 2-methoxyethyl,2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-isobutoxyethyl, 2- or3-methoxypropyl, 1-methoxyprop-2-yl, 2-or 3-ethoxypropyl or 2-or3-propoxypropyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 4,8-dioxadecyl, 4,6-dioxaundecyl, 3,6,9-trioxaundecyl,4,7,10-trioxaundecyl, 4,7,10-trioxadodecyl, 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-cyclohexyloxyethyl,2- or 3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, 2-phenoxyethyl,2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl,2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or3-butoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl,2-cyanoethyl, 2- or 3-cyanopropyl, 4-cyanobutyl, 2-cyclohexylalkyl, 2-or 3-cyclohexylpropyl, benzyl, 1- or 2-phenylethyl, cyclopentyl,cyclohexyl, cycloheptyl, phenyl, 2-methylphenyl, 4-methylphenyl,4-ethylphenyl, 4-isopropylphenyl, 4-butylphenyl, 2,4-dimethylphenyl,2,4,6-trimethylphenyl, 4 -cyanophenyl, 4-chlorophenyl,2,4-dichlorophenyl, 2-bromophenyl, 3-nitrophenyl, 4-nitrophenyl,prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl or but-3-en-1-yl.

Y is for example methylthio, ethylthio, propylthio, isopropylthio,butylthio, isobutylthio, pentylthio, hexylthio, phenylthio,2-methylphenylthio, 2-methoxyphenylthio, 2-chlorophenylthio, methoxy,ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy,isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, 2-methylpentyloxy,phenoxy, 2-, 3- or 4-methylphenoxy, 2-, 3- or 4-methoxyphenoxy, 2, 3- or4-chlorophenoxy, fluorine, chlorine or bromine.

R¹, R², R³, A¹, A², A³ and Y and also Z may each also be for examplemethylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl,butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, pentylsulfonyl,isopentylsulfonyl, neopentylsulfonyl, hexylsulfonyl, phenylsulfonyl,2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or2-chlorophenylsulfonyl.

A 5- or 6-membered saturated heterocyclic radical formed by Q² and Q²together with the nitrogen atom joining them, with or without furtherhetero atoms, is for example pyrrolidinyl, piperidinyl, morpholinyl,thiomorpholinyl, thiomorpholinyl S,S-dioxide, piperazinyl or N-(C₁ -C₄-alkyl)piperazinyl, such as N-methyl- or N-ethylpiperazinyl.

R¹, R², R³, A¹, A² and A³ may each also be for example formyl, acetyl,propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl,octanoyl, 2-ethylhexanoyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3- or4-methoxybenzyl or 2-, 3- or 4-chlorobenzoyl.

When Z is --CH═T, wherein T is derived from an acidic-CH compound H₂ T,suitable acidic-CH compounds H₂ T are for example compounds of theformulae IIa to IIg ##STR4## where L¹ is cyano, nitro, C₁ -C₄ -alkanoyl,substituted or unsubstituted benzoyl, C₁ -C₄ -alkylsulfonyl, substitutedor unsubstituted phenylsulfonyl, carboxyl, C₁ -C₄ -alkoxycarbonyl,phenoxycarbonyl, carbamoyl, C₁ -C₄ -mono- or -dialkylcarbamoyl,substituted or unsubstituted phenylcarbamoyl, substituted orunsubstituted phenyl, benzothiazol-2-yl, benzimidazol-2-yl,5-phenyl-1,3,4-thiadiazol-2-yl or 2-hydroxyquinoxalin-3-yl,

L² is C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

L³ is C₁ -C₄ -alkoxycarbonyl, phenylcarbamoyl or benzimidazol-2-yl,

L⁴ is hydrogen or C₁ -C₄ -alkyl,

L⁵ is hydrogen, C₁ -C₄ -alkyl or phenyl, and

L⁶ is C₁ -C₄ -alkyl.

Of particular suitability is a radical derived from the formula IIa orIIb where L¹ is cyano, C₁ -C₄ alkanoyl or C₁ -C₄ -alkoxycarbonyl, is C₁-C₄ -alkyl or C₁ -C₄ -alkoxy, and L³ is C₁ -C₄ -alkoxycarbonyl.

Of very particular suitability is a radical derived from the formula IIaor IIb where L¹ is cyano or C₁ -C₄ alkoxycarbonyl, L² is C₁ -C₄ -alkoxyand L³ is C₁ -C₄ -alkoxycarbonyl.

Preference is given to the azo dyes of the formula I where

X is cyano or a radical of the formula COOQ¹ where Q¹ is C₁ -C₄ -alkyl,

Y is C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulfonyl, chlorine,bromine, phenoxy, phenylthio or phenylsulfonyl,

Z is cyano, formyl or a radical of the formula --CH═T, wherein T is asdefined above, and

R¹, R² and R³ are each, independently of the others, C₁ -C₈ -alkyl,which may be substituted and may be interrupted by 1 or 2 oxygen atomsin ether function, C₅ -C₇ -cycloalkyl or C₃ -C₆ -alkenyl or R¹ and R²together are, together with the nitrogen atom joining them, a 5- or6-membered saturated heterocyclic radical with or without further heteroatoms.

Particular preference is given to azo dyes of formula I where

X is cyano,

Y is ethoxy, C₁ -C₄ -alkylthio, chlorine, bromine, phenoxy orphenylthio,

Z is formyl or a radical of formula ##STR5## where L¹ is cyano, C₁ -C₄-alkanoyl or C₁ -C₄ -alkoxycarbonyl, L² is C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, and L³ is C₁ -C₄ -alkoxycarbonyl, and

R¹, R² and R³ are each, independently of the others, C₁ -C₈ -alkyl,which may be substituted and may be interrupted by 1 or 2 oxygen atomsin ether function, or R¹ and R² together are, together with the nitrogenatom joining them, pyrrolidinyl, piperidinyl, morpholinyl, piperazinylor N-(C₁ -C₄ -alkyl )piperazinyl.

Of particular interest are azo dyes of formula I where X is cyano and Yis chlorine.

The azo dyes of the formula I can be prepared in a conventional manner.For example, the amine of the formula III ##STR6## where X, Y and Z areeach as defined above, can be diazotized in a conventional manner toform a diazonium salt which can then be coupled with a diaminopyridineof the formula IV ##STR7## where R¹, R² and R³ are each as definedabove.

It is also possible, however, to couple diazonium salts of diazocomponents of the formula IIIa ##STR8## where X and Y are each asdefined above, with the diaminopyridines IV to give the azo dyes of theformula I (Z=formyl ) and condense the resulting dyes with compounds ofthe formula H₂ T in a conventional manner.

The starting compounds III and IV are known per se or can be prepared bymethods known per se, as are described for example in EP-A-193 885 andU.S. Pat. No. 3,853,895.

We have also found that the dyeing of textile materials with azo dyes isadvantageously possible on using azo dyes of the formula Ia ##STR9##where X is cyano or a radical of the formula COOQ¹ or CONQ¹ Q², whereinQ¹ and Q² are identical or different and singly are, independently ofone another, substituted or unsubstituted C₁ -C₁₂ -alkyl with or withoutinterruption by from 1 to 3 oxygen atoms in ether function, C₅ -C₇-cycloalkyl, C₃ -C₄ -alkenyl, or substituted or unsubstituted phenyl ortogether are, together with the nitrogen atom joining them, a 5-or6-membered saturated heterocyclic radical with or without further heteroatoms or else Q² may be hydrogen,

Y is C₁ -C₆ -alkoxy, C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulfonyl, halogen,substituted or unsubstituted phenoxy, substituted or unsubstitutedphenylthio or substituted or unsubstituted phenylsulfonyl,

Z is cyano, nitro, substituted or unsubstituted phenylsulfonyl, C₁ -C₆-alkylsulfonyl, formyl or a radical of the formula--CH═T, wherein T isthe radical of an acidic-CH compound, and

A¹, A² and A³ are identical or different and singly are, independentlyof one another, substituted or unsubstituted C₁ -C₁₂ -alkyl, with orwithout interruption by from 1 to 3 oxygen atoms in ether function, C₅-C₇ -cycloalkyl, substituted or unsubstituted phenyl, C₃ -C₆ -alkenyl,substituted or unsubstituted benzoyl, C₁ -C₈ -alkanoyl, C₁ -C₆-alkylsulfonyl or substituted or unsubstituted phenylsulfonyl or A² andA³ together are, together with the nitrogen atom joining them, a 5- or6-membered saturated heterocyclic radical with or without further heteroatoms.

Suitable textile materials are for example polyesters in the various useforms (e.g. woven, knitted, yarn or fiber) or mixtures thereof withother fibers.

It is particularly advantageous to use the azo dyes of the formula Iatogether with UV absorbers. Suitable UV absorbers are for example thoseof the formula V or VI ##STR10## where E¹ is hydrogen or chlorine,

E² and E³ are identical or different and each is, independently of theother, hydrogen or C₁ -C₈ -alkyl which may be substituted by phenyl,

E⁴ is hydrogen or hydroxyl, and

E⁵ and E⁶ are identical or different and each is, independently of theother, hydrogen, hydroxyl, or C₁ -C₆ -alkoxy which may be substituted byhydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkanoyloxy or benzoyloxy.

Of particular suitability are UV absorbers of the formula Va, Vb, VIa orVIb ##STR11##

These UV absorbers can be used alone or else mixed with one another.More particularly, it is possible to use mixtures of different speciesof the formula V or VI or else mixtures of compounds of the formulae Vand VI.

In general, UV absorber is employed in an amount of from 1 to 8% byweight, preferably from 2 to 5% by weight, each percentage being basedon the weight of azo dye.

The azo dyes of the formula Ia have an advantageous application propertyprofile. More particularly, they have an excellent hot light fastness.They differ from the dyes disclosed in EP-A-201 896 in achieving anadvantageous degree of exhaustion.

The Examples which follow will further illustrate the invention.

GENERAL DYEING METHOD

This method is suitable for applying the dyes more particularlydescribed hereinafter.

10 g of polyester fabric are introduced at 50° C. into 200 ml of adyeing liquor containing 0.5% by weight, based on the polyester fabric,of a dye preparation and adjusted with acetic acid to pH 4.5. The fabricis treated at 50° C. for 5 minutes, the temperature of the liquor isthen raised over 30 minutes to 130° C. and maintained at that level for60 minutes, and the liquor is then cooled down over 20 minutes to 60° C.

The dyed polyester fabric is then reduction cleared by treating it at65° C. for 15 minutes in 200 ml of a liquor containing per liter 5 ml of30% strength by weight sodium peroxide solution, 3 g of sodiumdithionite and 1 g of an addition product of 48 mol of ethylene oxidewith 1 mol of castor oil. Finally, the fabric is rinsed, neutralizedwith dilute acetic acid, rinsed once more and dried.

The abovementioned dye preparation contains 40% by weight of azo dye and60% by weight of dispersant based on ligninsulfonate, each percentagebeing based on the weight of the preparation. The dye preparation mayadditionally contain from 1 to 8% by weight, based on the weight of azodye, of one of the above-described UV absorbers.

EXAMPLE 1

To 17.5 g of ice were added 94 g of concentrated sulfuric acid, and themixture was cooled down to 20° C. and then diluted with 15 g of glacialacetic acid. It was then cooled down to 0°-5° C. and32 g of 44% byweight of nitrosylsulfuric acid were added. To this mixture were added18.7 g of 2-amino-3-cyano-4-chloro-5-formylthiophene in the course ofabout 15 minutes with cooling at from 0° to 5° C.,and the reactionmixture was subsequently stirred at from 0° to 5° C. for 4 hours. Thesolution was stirred out onto a mixture prepared as follows:

37.6 g of the pyridine of the formula ##STR12##were dissolved in waterwith hydrochloric acid.

The solution was then cooled down with ice to from 0° to -5° C.

During the addition of the diazo component the temperature of thecoupling mixture was maintained with ice at ≦3° C. The pH was maintainedwith sodium acetate within the range from 0.3 to 2.0. The coupling wascomplete within a short time. The precipitated dye of the formula##STR13##was separated off, washed salt-free and dried.

This gave 50.7 g of the dye in the form of a dark red powder which dyespolyester in a bluish red shade.

The method of Example 1 also gives the dyes listed below in Tables 1 and2.

                                      TABLE 1                                     __________________________________________________________________________     ##STR14##                                                                    Ex. No.                                                                            R.sup.1     R.sup.2                                                                              R.sup.3   Hue on polyester                            __________________________________________________________________________     2   CH.sub.3    C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     3   C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     4   C.sub.3 H.sub.7 (n)                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     5   C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     6   CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     7   C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     8   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                     9   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    10   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    11   C.sub.2 H.sub.4 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    12   C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    13   C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    14   C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    15   C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    16   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 C.sub.6 H.sub.5                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    17   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    18   C.sub.3 H.sub.6 OC.sub.6 H.sub.11                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    19   C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    20   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    21   C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    22   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    23   C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    24   CH.sub.2 CH(OH)C.sub.6 H.sub.5                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    25   C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    26   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    27   C.sub.4 H.sub.8 OH                                                                        C.sub. 2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         bordeaux                                    28   C.sub.2 H.sub.5                                                                           (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      bordeaux                                    29   CH.sub.2 CHCH.sub.2                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      bordeaux                                    30   C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         bordeaux                                    31   C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    32   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    33   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.7 (n)                                                                     bordeaux                                    34   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    35   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                CH.sub.3                                                                             CH.sub.3  bordeaux                                    36   C.sub.3 H.sub.6 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  bordeaux                                    37   C.sub.2 H.sub.4 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  bordeaux                                    38   CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            CH.sub.3                                                                             CH.sub.3  bordeaux                                    39   CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    40   CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    41   C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         bordeaux                                    42   C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    43   C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    44   CH.sub.2 CHCH.sub.2                                                                       CH.sub.3                                                                             CH.sub.3  bordeaux                                    45   CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    46   CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    47   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    48   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         CH.sub.3                                                                             C.sub.2 H.sub.5                                                                         bordeaux                                    49   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         CH.sub.3                                                                             C.sub.3 H.sub.7 (n)                                                                     bordeaux                                    50   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               bordeaux                                    51   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    52   CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    53   CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    54   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         bordeaux                                    55   C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    56   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               bordeaux                                    57   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               bordeaux                                    58   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              bordeaux                                    59   CH(CH.sub.3)CH.sub. 2 OCH.sub.3                                                           C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              bordeaux                                    60   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               bordeaux                                    61   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               bordeaux                                    62   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               bordeaux                                    63   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                               bordeaux                                    __________________________________________________________________________

                  TABLE 2                                                         ______________________________________                                         ##STR15##                                                                                                        Hue on                                    Ex. No. R.sup.1        W            polyester                                 ______________________________________                                        64      C.sub.2 H.sub.4 OH                                                                            ##STR16##   bordeaux                                  65      C.sub.3 H.sub.6 OH                                                                            ##STR17##   bordeaux                                  66      C.sub.3 H.sub.6 OCH.sub.3                                                                     ##STR18##   bordeaux                                  67      C.sub.3 H.sub.6 OCOCH.sub.3                                                                   ##STR19##   bordeaux                                  68      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                    ##STR20##   bordeaux                                  69      C.sub. 3 H.sub.6 OC.sub.4 H.sub.8 OH                                                          ##STR21##   bordeaux                                  70      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                             ##STR22##   bordeaux                                  71      C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                           ##STR23##   bordeaux                                  72      CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                ##STR24##   bordeaux                                  ______________________________________                                    

EXAMPLE 73

4.6 g of the dye of the formula ##STR25##(Example 19) were stirred for24 hours at room temperature in 80 ml of propanol together with 1.32 gof malodinitrile and 1.0 g of sodium acetate. This is followed byfiltering off with suction, washing with propanol and drying. This gave5.0 g of the dye of the formula ##STR26##which dyes polyester materialin a blue shade of very good fastness.

EXAMPLE 74

5.34 g of the dye of the formula ##STR27##(Example 8) were reacted with4.23 g of butyl cyanoacetate as described in Example 73. This gave 5.8 gof the dye of the formula ##STR28##which dyes polyester material in afast blue shade.

EXAMPLE 75

240 ml of glacial acetic acid and 80 ml of propionic acid were mixed andcooled down to 0° C. 80 g of 80% by weight sulfuric acid were thenadded. Then 29.1 g of the diazo component of the formula ##STR29##wereadded at from -3° to +3° C. in the form of a finely ground powder. Themixture was stirred at from -3° to ±5°C. for 15 minutes, at which point33 g of 42% by weight nitrosylsulfuric acid were added dropwise at thattemperature with cooling and thorough stirring in the course of from 15to 20 minutes. The reaction mixture was subsequently stirred at from 0°to 5° C. for 2.5 hours and then combined with a 0°-5° C. solution of30.3 g of the coupling component of the formula ##STR30##in 200 ml ofglacial acetic acid and 50 ml of propionic acid. Then 90 g of anhydroussodium acetate were added with stirring at from 0° to 5° C. Theresulting dye of the formula ##STR31##was precipitated with water andisolated. It constituted 56 g of a bluish black powder which gives ablue solution in N,N-dimethylformamide and dyespolyester fabric in ablue shade having very good fastness properties.

The method of Examples 73 to 75 can be used to obtain the dyes listedbelowin Tables 3 and 4.

                                      TABLE 3                                     __________________________________________________________________________     ##STR32##                                                                                                             Hue on                               Ex. No.                                                                            R.sup.1     R.sup.2                                                                              R.sup.3   V      polyester                            __________________________________________________________________________     76  CH.sub.3    C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  77  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  78  C.sub.3 H.sub.7 (n)                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  79  C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  80  CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  81  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  82  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  83  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  84  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  85  C.sub.2 H.sub.4 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  86  C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  87  C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  88  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  89  C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  90  C.sub.3 H.sub.6 C.sub.2 H.sub.4 C.sub.6 H.sub.5                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  91  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  92  C.sub.3 H.sub.6 OC.sub.6 H.sub.11                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                  93  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                  94  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                  95  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                  96  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOH   blue                                  97  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CONH.sub.2                                                                           blue                                  98  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CONHCH.sub.3                                                                         blue                                  99  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 100  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 101  C(CH.sub.3).sub.3                                                                         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 102  C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 103  CH.sub.2 CH(OH)C.sub.6 H.sub.5                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 104  C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 105  C.sub.4 H.sub.8 OH                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     Blue                                 106  C.sub.2 H.sub.5                                                                           (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      CN     blue                                 107  CH.sub.2 CHCH.sub.2                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      CN     blue                                 108  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 109  C.sub.3 H.sub. 6 OC.sub.2 H.sub.4 OCH.sub.3                                               C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.7 (n)                                                                     CN     blue                                 110  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 111  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                CH.sub.3                                                                             CH.sub.3  CN     blue                                 112  C.sub.3 H.sub.6 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  CN     blue                                 113  C.sub.2 H.sub.4 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  CN     blue                                 114  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            CH.sub.3                                                                             CH.sub.3  CN     blue                                 115  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 116  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 117  C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 118  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 119  CH.sub.2 CHCH.sub.2                                                                       CH.sub.3                                                                             CH.sub.3  CN     blue                                 120  CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 121  CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 122  C(CH.sub.3).sub.3                                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 123  CH.sub.3    C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 124  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 125  C.sub.3 H.sub.7 (n)                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 126  CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 127  C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 128  CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 129  C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.5 OCH.sub.3                                                            C.sub. 2 H.sub.4 OCH.sub.3                                                              COOC.sub.2 H.sub.5                                                                   blue                                 130  C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.3 H.sub.7                                                                   blue                                 131  C.sub.2 H.sub.4 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.3 H.sub.7                                                                   blue                                 132  C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 133  C.sub.2 H.sub.4 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 134  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 135  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 136  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOH   blue                                 137  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONH.sub.2                                                                           blue                                 138  C.sub.2 H.sub.5                                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONHCH.sub.3                                                                         blue                                 139  C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 140  C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOH   blue                                 141  C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONHCH.sub.3                                                                         blue                                 142  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOH   blue                                 143  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONH.sub.2                                                                           blue                                 144  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONHCH.sub.3                                                                         blue                                 145  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 146  C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 147  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 C.sub.6 H.sub.5                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 148  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 149  C.sub.3 H.sub.6 OC.sub.6 H.sub.11                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 150  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 151  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 152  C(CH.sub.3).sub.3                                                                         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 153  C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 154  CH.sub.2 CH(OH)C.sub.6 H.sub.5                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 155  C.sub.3 H.sub.6 OCH.sub.2 C.sub.6 H.sub.5                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 156  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 157  C.sub.4 H.sub.8 OH                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 158  C.sub.2 H.sub.5                                                                           (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      COOC.sub.2 H.sub.5                                                                   blue                                 159  CH.sub.2 CHCH.sub.2                                                                       (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                   (C.sub.2 H.sub.4 O).sub.2 CH.sub.3                                                      COOC.sub.2 H.sub.5                                                                   blue                                 160  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 161  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.3 H.sub.7 (n)                                                                  C.sub.3 H.sub.7 (n)                                                                     COOC.sub.4 H.sub.9                                                                   blue                                 162  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 163  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                CH.sub.3                                                                             CH.sub.3  COOC.sub.4 H.sub.9                                                                   blue                                 164  C.sub.3 H.sub.6 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  COOC.sub.4 H.sub.9                                                                   blue                                 165  C.sub.2 H.sub.4 OCH.sub.3                                                                 CH.sub.3                                                                             CH.sub.3  COOC.sub.4 H.sub.9                                                                   blue                                 166  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            CH.sub.3                                                                             CH.sub.3  COOC.sub.4 H.sub.9                                                                   blue                                 167  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 168  CH(C.sub.2 H.sub.5)CH.sub.2 OH                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 169  C.sub.3 H.sub.6 OH                                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 170  C.sub.3 H.sub.6 OCOCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOCH.sub.3                                                                          blue                                 171  CH.sub.2 CHCH.sub.2                                                                       CH.sub.3                                                                             CH.sub.3  COOC.sub.4 H.sub.9                                                                   blue                                 172  CH.sub.2 CHCH.sub.2                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 173  CH.sub.2 CH(CH.sub.3)OCOCH.sub.3                                                          C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 174  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         CN     blue                                 175  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 176  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 177  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOH   blue                                 178  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         CONHCH.sub.3                                                                         blue                                 179  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 180  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOH   blue                                 181  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CONH.sub.2                                                                           blue                                 182  C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CONHCH.sub.3                                                                         blue                                 183  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub. 2 H.sub.5                                                                        CN     blue                                 184  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 185  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 186  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         COOH   blue                                 187  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         CONH.sub.2                                                                           blue                                 188  C.sub.2 H.sub.5                                                                           C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                         CONHCH.sub.3                                                                         blue                                 189  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 190  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 191  C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CONHCH.sub.3                                                                         blue                                 192  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 193  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 194  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 195  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 196  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 197  CH(CH.sub.3)C.sub.2 H.sub.5                                                               C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 198  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         CN     blue                                 199  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                   blue                                 200  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                         COOC.sub.4 H.sub.9                                                                   blue                                 201  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               CN     blue                                 202  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 203  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 204  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              CN     blue                                 205  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              COOC.sub.2 H.sub.5                                                                   blue                                 206  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              COOC.sub.4 H.sub.9                                                                   blue                                 207  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 208  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 209  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 210  C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               CN     blue                                 211  C(CH.sub.3).sub. 2 C.sub.2 H.sub.5                                                        C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 212  C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                         C.sub.2 H.sub.4 OCH.sub.3                                                            C.sub.2 H.sub.4 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 213  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               CN     blue                                 214  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 215  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 216  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              CN     blue                                 217  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                              COOC.sub.2 H.sub.5                                                                   blue                                 218  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.6 OCH.sub.3                                              COOC.sub.4 H.sub.9                                                                   blue                                 219  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub. 6 OC.sub.2 H.sub.4 OC.sub.2                                    H.sub.5   CN     blue                                 220  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               COOC.sub.2 H.sub.5                                                                   blue                                 221  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.7                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               COOC.sub.4 H.sub.9                                                                   blue                                 222  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               CNsub.5                                                                              blue                                 223  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               COOC.sub.2 H.sub.5                                                                   blue                                 224  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.2 H.sub.5                                                                      C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.2                                               COOC.sub.4 H.sub.9                                                                   blue                                 225  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                               CN     blue                                 226  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.2 H.sub.5                                                                   blue                                 227  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                            C.sub.3 H.sub.6 OCH.sub.3                                                               COOC.sub.4 H.sub.9                                                                   blue                                 __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR33##                                                                                                      Hues on                                     Ex. No.                                                                            R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                             W          polyester                                   __________________________________________________________________________    228  C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            ##STR34## blue                                        229  C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            ##STR35## blue                                        230  C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.2 H.sub.5                                                                      ##STR36## blue                                        231  C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.3 H.sub.6 OCH.sub.3                                                           C.sub.2 H.sub.5                                                                      ##STR37## blue                                        232  C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.4 OCH.sub.3                                                           C.sub.2 H.sub.4 OCH.sub.3                                                            ##STR38## blue                                        __________________________________________________________________________

We claim:
 1. A process for dyeing and printing textile materials with azo dyes, which comprises applying thereto an azo dye of the formula Ia ##STR39## where X is cyano or a radical of the formula COOQ¹ or CONQ¹ Q², wherein Q¹ and Q² are identical or different and singly are, independently of one another, substituted or unsubstituted C¹ -C¹² -alkyl with or without interruption by from 1 to 3 oxygen atoms in ether function, C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl, or substituted or unsubstituted phenyl, or together are, together with the nitrogen atom joining them, a 5- or 6-membered saturated heterocyclic radical with or without further hetero atoms or else Q² may be hydrogen,Y is C₁ -C₆ -alkylthio, C₁ -C₆ -alkylsulfonyl, halogen, substituted or unsubstituted phenoxy, substituted or unsubstituted phenylthio or substituted phenylsulfonyl, with the proviso that Y is not --Br, Z is cyano, nitro, substituted or unsubstituted phenylsulfonyl, C₁ -C₆ -alkylsulfonyl, formyl or a radical of the formula --CH═T, wherein T is the radical of an acidic-CH compound, and A¹, A² and A³ are identical or different and singly are, independently of one another, substituted or unsubstituted C₁ -C₁₂ -alkyl, with or without interruption by from 1 to 3 oxygen atoms in ether function, C₅ -C₇ -cycloalkyl, substituted or unsubstituted phenyl, C₃ -C₆ -alkenyl, substituted or unsubstituted benzoyl, C₁ -C₈ -alkanoyl, C₁ -C₈ -alkylsulfonyl or substituted or unsubstituted phenylsulfonyl, or A² and A³ together are, together with the nitrogen atom joining them, a 5- or 6-membered saturated heterocyclic radical with or without further hetero atoms.
 2. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR40##
 3. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR41##
 4. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR42##
 5. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR43##
 6. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR44##
 7. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR45##
 8. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR46##
 9. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR47##
 10. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR48##
 11. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR49##
 12. The process for dyeing and printing textile materials according to claim 1, wherein the azo dye of the formula Ia is ##STR50## 